Insecticide



Patented May 30, 1939 'l-' l i ffum'rao sra'ras PATENT OFFICE a- Claims.

This invention relates to an insecticide and more particularly to an insecticide composition comprising a terpene ether.

1 have found that terpene ethers, either alone or admixed with other materials are eilectlve insecticides. I have found the very surprising iact that mixtures oi terpene ethers with certain other insecticidal materials have tar greater toxic action on insects than oi either component of the mixtures alone. Terpene ethers have, then, a definite activatina action on other insecticidal materials. I have also found that certain of the terpenc ethers have a deiinite action in preventing the deterioration of other insecticides, such as. ior example, the active principles of pyrcthrum and rotenone bearing plants; etc., and

I prolonging their useful life.

The composition in accordance with this invention will comprise a terpcne ether and a diluent. Thediluent may be'another toxic materiai,' an admixture oi other toxic materials. an inert carrier material, or an admixture oi another toxic material and an inert carrier. The composition, in accordancewith my invention, which I prefer is one comprisine a terpene ether and another toxic material. admixed with an inert carrier material or suitable for admixture with an inert carrier material at the point oi'appliration.

The toxic material addedto thcterpenc ether,

where such is added, will be added in amountnecessary to have the desired toxicity to insects and may be, for example, a contact poison to insects. Furthermore, it may be a synthetic com- Dound or the active principles-oi a plant body. Suitable toxic materials for addition to the terpene other are, (or example, the active principles oi pyrethrum or r'otenone bearing plants; nicotine; nicotine compounds, as. nicotine suiiate,

cte.; aliphatic thiocyanates, etc.

The inert carrier selected tor use in composilions according to this invention may be varied.

depending upon the method of application by '.\\-hicli. and the purpose [or which. the composilion will ultimately be used. The composition in accordance with this invention can be used as a spray, a dusiimz powder, or asa paint or gum. The inert carrier used in compositions intended [or application as a spray will be a liquid of the Friar ll. Thompson. In. Wilmington. Dd.. aaliner to Hercules Powder Company, Wllmlnytan, Del.. a corporation of Delaware Na Drawing. Application April 28, 1931.

I Serial No. 139.612

Compositions for application as a spray may be utilized in the term of a solution or suspension. Such compositions will comprise a terpene ether,

or a 'terpene ether and another insecticidal materiai, dissolved, or partially dissolved and partially suspended, in an inert carrier liquid which is a solvent for one or more of the active ingredicnts of the composition, such as, for example, a petroleum hydrocarbon fraction. as. deodorizcd or ordinary kerosene, etc. Such compositionsare suitable for use in the control 0! insects, such as, flies, mosquitoes, roaches, bedbucs, fleas, silver hsh. etc., intestine public buildings, restaurants, hotels, dwellings, warehouses, etc.

A typical composition of this type will consist of a. solution prepared by dissolving the extractives of 1 pound of pyrethrum flowers in 1 gallon of a liquid containing 5%, by volume, of a terpene ether and 95%, by volume, of deodorized kerosene.

It will be appreciated that this composition is elven merely by way of example and that the terpene other, the other insecticide present and the carrier may be varied both as to the exact material used and as to the relative proportions uscd,,in any desired manner depending .upon the spray.

Compositions at this type may be prepared in "anilin handling can frequently be obtained. and such concentrates are within the scope of my invention. Concentrated extracts may be prepared by the direct extraction of py'rethrum ilowers with a tcrpene ether or with a mixture consisting of a tcrpene ether and another extractor. Concentrates prepared in this way may be further diluted immediately after preparation. or at the point of use, as may be desired.

Compositions for application as a spray may also be utilized in the form of an aqueous emulsion. Such compositions will comprise a terpene ether. and desirably another insecticidal material, emulsified in water. Such emulsions will contain an emulsifying agent, such as. for example. a soap, -a sulfonated oil, etc. They may be prepared in completely finished form at the point of manufacture. or they may be prepared in the form of a concentrate comprising a terpenc ether. another insecticidal material and an emulsifying agent, and then diluted and emulsiiled with water at the point of application. By the latter procedure unnecessary packaging, transportation and handling of water is avoided, the advantages of which are readily apparent. Emulsifled compositions of this type are advantagcous for the destruction. of insects attacking horticultural plants. such as, for example, the various kinds of plant lice. mea-ly buss. thrips. the various kinds of scale insects. etc.

An emulsified insecticidal composition of a somewhat different type. but likewise advantageous for the destruction of insects on horticultural plants may also be prepared in accordance with this inventioni This composition will comprise a tcrpene ether and a. petroleum hydrocarbon oil of suitable viscosity say, of 30 see. iSaybolt at I00 F.) or above, emulsified in water with the aid of an emulsifying agent. a composition the tcrpene ether enhances the insecticidal action of the oil.

The insecticidal]composltionsj in accordance with thisinventlon, may also be used for the destruction of "insects whichattack agricultural .or horticultural plants, in the form of an insectiwith 19'. by weight. of a tcrpene ether and 1%.

by weight, nicotine. I

This composition is given merely as an illus tration of my invention, and it will be appreciatcd that other insecticidal materials may be used instead of the nicotine, and other carriers used to replace the tale. it will also be under stood that the proportions of the ingredients may be varied to suit the purpose for which the dust is lnt ended. Thus, higher concentrations of the tcrpene ether and of the nlcotineor other insecticidal material may be addedto the pow-' dereo carrier. if a more toxic material is desired for a speciiic application or if the composition is intended to be diluted'at the point of n'pplication by the addition of more powdered carricr. it will. of course, be appreciated that the maximum amount of the terpeueether and the hydric alcohol or a polyhydric alcohol.

In such other insecticidal material added is fixed by the inherent limitation that the dust must be freeilowlng so that it may be readily applied to plants.

A highly active insecticidal dust of a somewhat different type may also be prepared in accordance with this invention. Such a dust will comprise a terpene ether incorporated into a powdered insecticidal material such as, for example, ground pyrcthruin tiowcrs, powdered derris root, powdered cube, etc.

The tcrpene ethers used in the compositions in accordance with this invention are chnractcr-' ized by containing an other linkage connecting a terpcnic group with another group, and maybe prepared in either of two ways. They may be prepared by the etlieriflcntion of the hydroxyl group of a terpene alcohol with another alcohol, or they may be prepared by the direct odditlon of an alcohol to a. double bond of an unsaturated tcrpene compound. The latter type ethers will, for convenience, be termed "additive" tcrpene others. -The alcohol used as the etherifying agent may. in either method, be a mono- The monoliydric alcohol may be, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl nlcohol, amyl alcohol, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monoethyl ether, etc. The polyhydric alcohol may be, for-example, ethylene glycol, diethyiene glycol, glycerol, etc.

The tcrpene alcohol used to prepare a tcrpene ether by the ether'iflcation of its hydrokyl group may be any tcrpene alcohol having a reactive hydroxyl group.'such as, for example, alpha. lerpineol. borneol, fenchyl alcohol, etc. Crude tcrpene cuts rich in tcrpene alcohols may likewise be etherlfied. Such others may be readily prepared by well known methods.

The unsaturated tcrpene compound used to prepare a tcrpene other by the addition of an alcohol at n double bond may be, for example, alpha pinene,- noplnene, dlpentcne, terpincnc, tcrpinolene, phcllandrenc, sylvestrcne, alpha, terpincol, beta'terpineol, carenc, cnmphenc, bornylene, etc. These tcrpene compounds do not need to be in pure form, but may be reacted in the form-of erude'mixtures. Thus, in place of the several pure tcrpene compounds, crude natural mixtures, as for example, turpentine, pine oil, etc., or crude fractions of the mixtures may be rcaciedwithout the necessity of isolating the rc suiting others in their pure state, for use in the .inscciicdal compositions in accordance with this invention. The resulting mixtures of tcrpene others may, and fr'om.the standpoint of economy will desirably be used per se in my insecticidal compositions where herein a tcrpene cthcr'is specified, it will be understood to mean either a purccompound or n mixture prepared. from a vmixed tcrpene fraction.

The addition of an alcohol to the double bond of an unsntumted tcrpene for the production of till beta excess oi molecular proportions. "nuts. to

- preferably within the ranee oi about i% to on-the same basis.

Household fly sprays as hcrctoiore prepared couuunnly consist of a kerosene extract oi pyrt-thrum flowers which is diluted to contain approximately the extra'etivea at l pound oi pyrcthiliill flowers in l'gallon oi kerosene, which may be rieortnrized or straight cut.' The only additions in this material would be the use at some periiuniue material to counteract the odor of the kerosene. The pyrctiiriu content oi a spray .-;atisiactory of this type is usually adjusted according to the quality at the pyrcthrum flowers. Some sprays may contain as much as the extractives oi 1% pounds or il poundsoi flowers. These sprays may be alsov manufactured by diluting pyrethrum concentrates in kerosene, for example, the common iormula in the industry is 6% oi a zl m'rethrum extract and 05% oi kerosene. This mixture or composition is generally considered a insecticide. In the "Feet-Grady method" at testing fly sprays. a kill of [ram 60% to 70% with this iormula is considercdsattsiuclory. Another-method which is sometimes llscrl for testing insecticides at this type and which gives much lower results I is the "Campbell method" oi testing.

The insecticidal compositions, in accordance with this invention, and their advantages over prior art compositions may be more specifically illustrated by the iollowing:

A series of insecticidal compositions containinc diiiercnt amounts of the tetpene ether produced by ihe direct addition oi ethylene glycol to the unsaturated compounds contained in sum turpentine, were prepared. These insecticidal composiicns consisted of solutions of the extractircs of i l, pounds at pyrethrnm flowers dissolved in a gallon oi deodorizcd kerosene. containing the percentages of the ierpene ethers shown in the table below. The toxic action at each oi these solutions to house file's was tested by the "Campbell method" with, the results tabulated 55 in theiollowing table:

. Table I l't-nvat 'lotal ieicent i'rrrent I irrP-mnumber ii un in dead It A at ten: iiia uituulra imp" ii if lill ll 15 w int i? so am up a: 7.5 -W2 lill Iii are im no at 12.: no an I in 'lh." up; I'll 7t Further tests on these compositions were by the "Pect-Qradymetlrod" to further show the degree of activity exhibited by the terpenc ether. The results oi these tests are shown in the iollowing table:

' moeuwa- Table i! Total Percent Percent I Percent iarneaa other number dawn to dead 2i flies minutes hours ittll il7. till it?" ilii Si tut-. mt at Wt i J no The results presented in Tables I and II deiiniteiy show the marked increase in the lnsccticidul activity oi the toxic principles oi pyrethrum flowers by a terpene ether. Thus, it will be noted in Table I that the presence at 15% oi the terpcne ether in the composition increased the per cent kill in 24 hours approximately five-told by the "Campbell method" at testing. In Table 11 it will be observed that comparable results were obtained by the "Poet-Grady mcthod'foi testing. These tables illustrate the efliciency oi the terpcnc other; in activating another insecticidal material in a .fly spray. Test on other types of insecticidal compositions have shown comparable increases in efliciency.

it will be appreciated irom this illustration that by the addition of a terpene ether, an insecticide is obtained which has greater toxic action on insects than the same insecticide not containing a tcrpene ether. It will be iurtherappreciated that insecticidal compositions can be made more dilute the same insecticide not containing a terpe'nc other. e

The insecticidal compositions in accordance with this invention and their advantages over prior art compositions-are further illustrated by the following: 4

The activating action oi the tcrpene ethers ,was compared with that oi pine oil by test on a series of compositions containing, respectively, pine oil, the additive methyl ether oi tcrpinoienc, and the additive ethylene glycol ether of turpen- The estratires at at its. at pyn-tltnun flowers in our eailoa oi kerosene.

Each at these compositions was tested for toxicity to house flies by the "Peebfirbdy method" of testing. with the ioilow'ingresuits:

Table IV Nu. oi Knochioa'u Kill-iii um in iii mm. .i an.

I'nruii Iurru! A pineoii)................. Lilia W a A 5.0 additive tuethyietiterol terplnt-oil lil;l \iti so A (ii-1. tnitiiiirr ethylene Piyrill rtiu'r oi tur wuliuel.... lull in II II (ifi'l. pine uill 7iil 3 lill 17 it t 15" ail-intro methyl ether oi trrpiuruil 75.- itll 4 ll till";n-tiiitirtwthyiena yirol other 0! turpentine). L33 it!) for a given killim: power than of six months.

in the above table it will be noted that the terpene ethers contributed a definitely greater tnxicltyto the compositions tested than did the pine oil. Thus, in the B formulas. the composition containing l5% pine oil actually killed only 47% oi the tiles in 24 hours. while the corresponding compositions containing the terpene ethers, made in accordance withthis invention, killed 78% and 94%, respectively.

As mentioned hereinbeiore certain terpene others have, in addition to a deiinite activating action, a remarkable preservative action against deterioration by sunlight for other insecticides. such as, for example, the active principles of pyr'ethrum, and rotenone bearing plants, etc. This preservative action isillustrated by the following:

Two samples of an insecticldecomposltion having the-following i'ormula were prepared:

Per cent by volume :1 extract-oi pyrethrum flowers in kerosene 5 "iinvsirncilm-a uLL'il lint. or pyrcillruln ilnu'i-ni in i Onesamplc was prepared and stored in a clear flint glass bottle in diffusedaylight for a period At the end oi this period the second sample was prepared and both were then tested for toxicity to house flies by the "Pect- Grady" icst. The results of these tests follow:

. Tobie V No. oi tiles Knock-dawn Kill in used in til min. .i hrs.

' Inrnd Incrnl New simple 0i) iill tld Uliisnmplo an illl ill I lt' i s w ell known'that under similar conditions of exposure an ordinary py'rethrum extract will lose 50% of its insecticidal efllciency, so it will be, .-appreciated that the preservative action of the terpene ether exemplified by the above table is a i'cl'y definite improvement. 7

Insecticidal compositions in accordance with this invention, suitable for use as horticultural sprays, are illustrated by the following:

-A series of compositions oi the aqueous cmulsion type consisting oi a 20:l aicohoiic extract of pyretlirnm flowers diluted with lDOO parts of -\\'iltel,'(illl'l'l0nt percentages'ol the additive ethyienc glycol ether of turpentine. and 0.2% by weight ot potassium'olcatc. on the basis of the weight of v.ilteiinished "compositions. Two comparative compositions consisting oi a 202i alcoholic cx'- tract oi pyrc'thrum flowers (20 lbs. oi pyrethrtim flowers extracted by 1 gallon oi ethyl aicoholi diluted with i000'and 2000 parts 0! water, rc-

spot-lively. and 0.2% by weight of potasslumoicaie on the basis 0! the weight of lhe finished compositions. "Each'of these compositions was tested for toxicity to nasturtiurn aphis. The results of these tests aresummarized in the ioliowing table.

Table VI Num- Per- 13: he! cant Formula No. Composition dami killed horol mm" in 24 in ii hours hours (ontrul A... l: ltlll diluted pyrcihrurn Ila) Ml 0i mint-i: puissant in oleaic-il.." ll) u'cighl oi loinl mumosiiiun. i: am illlllltil pyrcillrum 002 Kill 55 (oniml ll...

. extract; potrmium uloaii--.'."T by weight oi iuiul eulmmsiiinn. Spray No.i.. lzamdiluicii pyn-ihruni rurucl; let-pone cilwr-- V 0.05% by wt. 0! total muninsiiiou; "WHIP." L",'{.

In the above table it will be noted that the addition of 0.05%, 0.10%, and 015%, respectively. of the additive ethylene glycol ether oi turpentine to the pyrethrum spray increased the kill by 12%, 21% and 38%, respectively. These increases in the percentage killed are quite marked, as will be appreciated when it is notedthat the kill was increased only 6% by doubling the pyrethrum content of control B, in control A.

It will be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as herein broadly described and claimed is in no way limited thereby.

It will be understood that the term additive terpene cthers"'os used in the claims designates a terpcne ether produced by the direct addition 0! an alcohol to an unsaturated tcrpene compound as herclnbciore described.

What I claim and desire to protect by Letters Patent is:

1. An insecticidal composition comprising an other of n terpeno and an alcohol.

2. An insecticidal composition comprising an additive ether oi a terpen'c and an alcohol.

3. An insecticidal-composition comprising an additive other 0! a terpene and an alcohol. a contact insecticide extracted from a plant body and a carrier.

4. An insecticidal composition comprising the additive ether of ethylene glycol and turpentine. aconiact insecticide extracted from a plant body and a carrier.

5. An insecticidal composition'comprising the additive ether of ethylene glycol and turpentine,

the extractives of pyrethrum flowers and a carrier.

additive et-hcr'oi ethylene glycoljand turpentine. rotcnonc. and a carrier.

7. An insecticide composition comprisin'g'an additive ether of a terp'ene and an aliphatic alcohol. acontact insecticide extracted from a plant body and a cnrricr.

8. An insecticidal composition comprising an.

additive other oi a terpen'c and an alcohol. and a powdered plant insecticidal material.

9. An insccticidalcomposition comprising the additive other of ethylene glycol and-turpentine. and powdered dcrris root.

FRIAR M. THOMPSON. Ja.

6. An insecticidal composition comprising the 

